CN114504952B - Double-sided conductive film filter assembly and water purifying method - Google Patents

Double-sided conductive film filter assembly and water purifying method Download PDF

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CN114504952B
CN114504952B CN202210298472.4A CN202210298472A CN114504952B CN 114504952 B CN114504952 B CN 114504952B CN 202210298472 A CN202210298472 A CN 202210298472A CN 114504952 B CN114504952 B CN 114504952B
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CN114504952A (en
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孙猛
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Tsinghua University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
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    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

A double-sided conductive film filter assembly and a water purifying method, wherein the double-sided conductive film filter assembly comprises a double-sided conductive filter film, and comprises: the porous membrane substrate and two layers of metal conductive coatings are respectively formed on two surfaces of the porous membrane substrate and used as a cathode and an anode connected to an external power supply; the feeding chamber and the infiltration chamber are respectively arranged at two sides of the double-sided conductive filter membrane; the two groups of conductive connecting pieces are respectively clamped between the double-sided conductive filter membrane and the feeding chamber and between the double-sided conductive filter membrane and the infiltration chamber and are used for electrically connecting the double-sided conductive filter membrane with an external power supply; and the sealing rubber ring is sleeved on the outer periphery of the double-sided conductive filter membrane and is used for preventing the feed liquid in the feed chamber and the infiltration chamber from seeping out from the outer periphery of the double-sided conductive filter membrane. The invention can fully exert the functions and characteristics of electrochemical negative and positive bipolar reactions, so that electrochemical oxidation and reduction reactions act on the upper and lower surfaces of the double-sided conductive filter membrane cooperatively, and the quick removal of various pollutants difficult to degrade in water is realized.

Description

Double-sided conductive film filter assembly and water purifying method
Technical Field
The invention relates to the fields of electrochemistry, membrane separation, water treatment and the like, in particular to a double-sided conductive filter membrane filter assembly and a water purifying method.
Technical Field
At present, one of the main methods of water treatment is a physical and chemical method. The physical and chemical method is to remove the pollutants in the water through physical and chemical actions such as adsorption, precipitation, oxidation reduction, filtration and the like, so as to achieve the aim of purifying the water quality. The membrane separation technology has simple operation, high efficiency and no phase change in the filtration process, and is commonly used for deep purification of water quality and recovery of sewage resources. However, in the long-term membrane filtration process, the large molecular substances trapped by the membrane can cause membrane pollution and membrane hole blockage, and trapped liquid can become concentrated water containing high-concentration pollutants, so that the treatment is difficult. Therefore, in order to keep stable operation of membrane filtration, a pretreatment process is required to be arranged before a membrane assembly and the membrane is backwashed periodically, so that the application cost of the membrane separation water purification technology is increased.
The conductive filter membrane is used as an emerging membrane material, can play an electrochemical water purifying role in the membrane filtering process, and has outstanding advantages in rapid and sustainable water quality purification. The space limiting effect of the micro-nano pore canal of the conductive filter membrane enhances the electron utilization efficiency of the electrochemical reaction, and active substances with strong water purifying capacity can be generated in situ selectively. To date, studies have reported that conductive membrane filtration water treatment techniques, but are limited to the implementation of electrochemical half reactions (cathodic reduction or anodic oxidation) using conductive filter membranes. When the unipolar single-sided conductive filter membrane is used for purifying water, a counter electrode is additionally arranged, the design difficulty of a membrane assembly is increased, the effect of electrochemical half reaction on the counter electrode is ignored, the utilization rate of electrons can be reduced, and the water purifying effect cannot be fully exerted.
Disclosure of Invention
Accordingly, it is a primary objective of the present invention to provide a double-sided conductive film filter assembly and a water purifying method, so as to at least partially solve at least one of the above-mentioned problems.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
as a first aspect of the present invention, there is provided a double-sided conductive film filter assembly comprising: a double-sided conductive filter membrane comprising: a porous membrane substrate, and two metal conductive coatings respectively formed on two surfaces of the porous membrane substrate for serving as a cathode and an anode connected to an external power supply; the feeding chamber and the infiltration chamber are respectively arranged at two sides of the double-sided conductive filter membrane; wherein the metallic conductive coating as a cathode faces the feed chamber and the metallic conductive coating as an anode faces the permeate chamber; two sets of electrically conductive connecting pieces, press from both sides respectively locate between two-sided electrically conductive filter membrane and the feed chamber and between two-sided electrically conductive filter membrane and the infiltration room, be used for with two-sided electrically conductive filter membrane with the external power source carries out the electricity and is connected, electrically conductive connecting piece includes: an annular conductive gasket, one surface of which is attached to the metal conductive coating, and an annular conductive sheet, one surface of which is attached to the other surface of the annular conductive gasket, and the other surface of which is attached to the feed chamber or the infiltration chamber; and the sealing rubber ring is sleeved on the outer periphery of the double-sided conductive filter membrane and is used for preventing the feed liquid in the feed chamber and the infiltration chamber from seeping out from the outer periphery of the double-sided conductive filter membrane.
As a second aspect of the present invention, there is provided a method for electrically filtering purified water using the double-sided conductive film filter assembly as described above, comprising: connecting the double-sided conductive filter membrane of the double-sided conductive membrane filter assembly to an external power supply through the two groups of conductive connecting pieces; charging feed liquid into a feed chamber, and carrying out electrofiltration treatment on the feed liquid by utilizing the double-sided conductive filter membrane; and outputting the treated feed liquid from the infiltration chamber.
Based on the technical scheme, the double-sided conductive film filter assembly and the water purifying method have at least one or a part of the following beneficial effects:
(1) According to the double-sided conductive film filter assembly, the two layers of metal conductive coatings of the double-sided conductive film can be connected to the anode and the cathode of an external power supply respectively through the conductive connecting piece, under the electrifying condition, the permeation direction of filtrate is parallel to the direction of an electric field, and active substances with strong oxidability are generated in situ by the double-sided conductive film based on the synergistic effect of electrochemical reduction and oxidation, so that various refractory organic pollutants in water can be rapidly degraded.
(2) According to the invention, the conductive connecting piece with a specific structure, namely the combined structure of the annular conductive gasket and the annular conductive sheet, is clamped between the double-sided conductive filter membrane and the feeding chamber and between the double-sided conductive filter membrane and the permeation chamber, and is matched with the sealing rubber ring, so that the integrated double-sided conductive membrane filter assembly with a compact structure is formed.
(3) The double-sided conductive film filter assembly provided by the invention not only can be applied to water quality purification in various scenes, but also can be widely applied to the fields of green organic synthesis, biomedical engineering and the like.
Drawings
FIG. 1 is a schematic diagram of a metal sputtering preparation method of a double-sided conductive filter membrane according to an embodiment of the invention;
FIG. 2A is a side exploded view of a double-sided conductive film filter assembly according to an embodiment of the present invention;
FIG. 2B is an exploded view of a double-sided conductive film filter assembly according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of an electrofiltration water purification process according to an embodiment of the present invention.
In the above figures, the reference numerals have the following meanings:
100. a double-sided conductive film filter assembly;
110. a double-sided conductive filter membrane;
111. 112 a metal conductive coating; 113. a porous membrane substrate;
120. a feed chamber;
130. a permeate chamber;
140. 140' annular conductive sheet;
150. a 150' annular conductive gasket;
160. sealing rubber rings;
200. an external power supply;
300. a power circulation device.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The invention provides a double-sided conductive film filter assembly and a water purifying method, wherein conductive coatings are formed on two surfaces of a porous film substrate through double-sided modification of the porous film substrate, so that a double-sided conductive filter film is obtained, two sides of the double-sided conductive filter film are connected to an external power supply through conductive connecting pieces, and the permeation direction of filtrate is parallel to the direction of an electric field under the condition of electrification, so that the functions and characteristics of electrochemical negative and positive bipolar reactions are fully exerted, the electrochemical oxidation and reduction reactions act on the upper surface and the lower surface of the double-sided conductive filter film cooperatively, active oxygen substances with strong oxidability are generated, and the quick removal of various water refractory pollutants is realized.
According to some embodiments of the present invention, there is provided a double-sided conductive film filter assembly 100, as shown in fig. 2A, 2B and 3, comprising: a double-sided conductive filter membrane 110, the double-sided conductive filter membrane 110 comprising a porous membrane substrate, and two metal conductive coatings 111, 112 formed on both surfaces of the porous membrane substrate as a cathode and an anode connected to an external power source 200, respectively; the feeding chamber 120 and the permeation chamber 130 are respectively arranged at two sides of the double-sided conductive filter membrane 110; wherein the metallic conductive coating 111 as a cathode faces the feed chamber 120 and the metallic conductive coating 112 as an anode faces the permeate chamber 130; the two sets of conductive connection pieces are respectively clamped between the double-sided conductive filter membrane 110 and the feeding chamber 120 and between the double-sided conductive filter membrane 110 and the infiltration chamber 130, and are used for electrically connecting the double-sided conductive filter membrane 110 with the external power supply 200, and the conductive connection pieces comprise: annular conductive washers 150, 150' having one surface thereof adhered to the metal conductive coatings 111, 112, and annular conductive sheets 140, 140' having one surface thereof adhered to the other surface of the annular conductive washers 150, 150' remote from the metal conductive coatings 111, 112, and the other surface thereof adhered to the feed chamber 120 or the permeate chamber 130; and a sealing rubber ring 160 sleeved on the outer periphery of the double-sided conductive filter membrane 110 for preventing the feed liquid in the feed chamber 120 and the permeate chamber 130 from seeping out from the outer periphery of the double-sided conductive filter membrane 110.
On the basis, on one hand, good electric connection can be realized through the fitting contact between the annular conductive gasket, the double-sided conductive filter membrane and the annular conductive sheet, and on the other hand, the metal conductive coatings 111 and 112 can be prevented from being worn. Under the condition of electrifying, the annular conductive gasket and the annular conductive sheet are utilized to uniformly apply voltage to the two metal conductive layers, the permeation direction of the filtrate is parallel to the electric field direction, the functions and the characteristics of electrochemical negative and positive bipolar reactions can be fully exerted, the electrochemical oxidation and reduction reactions act on the upper surface and the lower surface of the double-sided conductive filter membrane cooperatively, active oxygen substances with strong oxidability are generated, and the quick removal of various water refractory pollutants is realized.
In some embodiments, the annular conductive washers 150, 150 'may be made of conductive rubber, and the annular conductive plates 140, 140' may be made of stainless steel or other corrosion-resistant conductive materials, but are not limited thereto, and may be selected according to practical needs. In some embodiments, the annular conductive washers 150, 150' have a thickness of 0.2-2 mm; the thickness of the annular conductive sheets 140, 140' is 0.5-2 mm.
In some embodiments, the side of the feed chamber 120 and the top surface opposite the permeate chamber 130 are provided with a feed hole, respectively, and the side of the permeate chamber 130 and the bottom surface opposite the feed chamber 120 are provided with a feed hole, respectively. Wherein the feed chamber and permeate chamber feed holes can be plugged so that electrofiltration can be selectively performed in either cross-flow filtration or dead-end filtration.
Specifically, the feed holes on the side surfaces of the feed chamber and the permeation chamber are plugged, the top surface feed hole of the feed chamber is used for feeding water, and the bottom surface feed hole of the permeation chamber is used for outputting the treated feed liquid, and the electric filtration mode is dead-end filtration; when the holes on the side surface and the top surface of the feeding chamber are used for water inlet and water outlet, and the holes on the bottom surface or the side surface of the penetration chamber are used for outputting the treated feed liquid, the electric filtration mode is cross-flow filtration.
In some embodiments, the annular conductive plates 140, 140' have electrode posts extending therefrom either from the feed chamber 120 or the permeate chamber 130 for connection to an external power source 200.
In some embodiments, the porous membrane substrate has a micro-nano porous structure and may be selected from one of a ceramic membrane, a polytetrafluoroethylene membrane, a polyamide membrane, a polysulfone membrane, and the like.
Taking a ceramic membrane as an example, on one hand, the ceramic membrane has insulating property and certain thickness, and can be used as a membrane substrate to effectively separate cathode and anode materials and prevent the contact of two electrodes from generating short circuit; on the other hand, the ceramic membrane also has certain mechanical strength, and ensures the stability of the conductive filter membrane.
In some embodiments, the two metal conductive coatings may be the same or different, and are independently selected from Cu, pd, pt, au, or other materials, and may be specifically selected according to practical needs.
In some embodiments, the thickness of the metallic conductive coating is 10 to 60nm, preferably 20 to 50nm, and may be, for example, 20nm, 30nm, 40nm, etc.
In some embodiments, the two metal conductive coatings are sequentially formed on both surfaces of the porous membrane substrate using physical vapor deposition. The prepared double-sided conductive filter membrane has similar performances with a porous membrane substrate in pore size distribution, water flux and hydrophilicity.
In some embodiments, physical vapor deposition methods include magnetron sputtering, vacuum evaporation, arc plasma, and the like, including but not limited to. According to the invention, a metal conductive coating is formed on the surface of the porous membrane substrate in a physical vapor deposition mode, and nano metal can be dispersed and uniformly deposited on the surface of the membrane substrate, so that the metal nano coating is formed on the surface of the porous membrane substrate, and the requirements on catalytic activity and conductivity in the electrofiltration process are met.
In some embodiments, a confocal magnetron co-sputtering technique is used to form the metal conductive coating, and in some embodiments, a ceramic film is taken as an example, and the method mainly comprises the following steps S11 to S14:
step S11: the basic pressure in the sputtering chamber of the confocal magnetron co-sputtering device is kept to be 10 -7 The vacuum environment of Pa uses ultra-pure argon gas to provide working pressure of 0.3Pa so as to remove the possible pollution in the sputtering chamber, remove the residual air and prevent the oxidation of the metal functional surface.
Step S12: the ceramic film was placed on a silicon support and the metal sputtering target of the confocal magnetron co-sputtering apparatus was placed horizontally opposite the ceramic film as shown in fig. 1.
In some embodiments, the ceramic membrane in step S12 has been pre-treated to ensure the reliability of the prepared membrane, the pre-treatments for example specifically comprising: the ceramic membrane is cleaned by deionized water for 1 to 5 times, soaked in ultrapure water for 12 to 24 hours and preserved at a temperature of between 1 and 4 ℃.
In some embodiments, the parameters of the ceramic membrane may be, for example: the molecular weight cut-off is 200-400 kDa, the diameter is 10-55 mm, the thickness is 1.0-5.0 mm, and the main component is TiO 2 And ZrO(s) 2 。
In some embodiments, the ceramic membrane in step S12 may be wrapped with a sealing membrane to cover the sides of the ceramic membrane before being placed on the silicon stent.
In some embodiments, the sputtering angle of the metal sputtering target and the ceramic film in step S12 is controlled to be 20 to 40 ° and the distance is 15 to 20cm, as shown in fig. 1.
Step S13: and uniformly sputtering metal onto one surface of the ceramic film to disperse and uniformly deposit nano metal on the surface of the ceramic film to form a metal conductive coating.
Step S14: inverting the ceramic film in step S13 so that one surface of the non-sputtered metal faces the metal sputtering target, repeating the operation of step S13 so that a metal conductive coating is formed on the other surface of the ceramic film.
In some embodiments, the confocal magnetron sputtering device in steps S13 and S14 applies a bias of 20-60W and a deposition rate of 1.0-5.0 nm min -1 。
In some embodiments, the surface metal sputtering thickness is controlled in steps S13 and S14 by a quartz thickness gauge to 10 to 60nm. After the sputtering is finished, a layer of metal coating film with different colors from the original ceramic film can be observed to be uniformly adhered on the surface of the ceramic film.
There is also provided, in accordance with some embodiments of the present invention, a method of electrically filtering clean water using the double-sided conductive film filter assembly 100 as described above, comprising the steps of S21 to S23:
step S21: the double-sided conductive filter membrane 110 of the double-sided conductive filter membrane module 100 is connected to the external power supply 200 through two sets of conductive connection pieces;
in some embodiments, step S21 specifically includes: the two metal conductive coatings 111, 112 of the double-sided conductive filter membrane are connected to the cathode and anode of the direct current power supply through conductive connectors, respectively.
Step S22: charging feed liquid into the feeding chamber 120, and carrying out electrofiltration treatment on the feed liquid by using the double-sided conductive filter membrane 110 under the condition of electrification;
in some embodiments, the feed solution in step S22 flows through the double-sided conductive filter membrane 110 in a cross-flow filtration or dead-end filtration mode. Specifically, the filtration mode is switched by controlling the communication state of the feed holes of the feed chamber 120 and the permeate chamber 130.
For example, by selecting a cross-flow filtration osmosis mode, the feed liquid flows in a direction parallel to the membrane surface, so that the water flux of the double-sided conductive filter membrane 110 is kept at a constant value, which can slow down the membrane pollution and blocking problems, prolong the service life of the membrane, and simultaneously ensure that the concentration of pollutants is kept constant when the percolate passes through the membrane layer.
More specifically, the feed liquid can be at a pressure of 0.05-0.5 bar for 0.05-5.0L min -1 Is circulated through the feed chamber.
In some embodiments, step S22 uses the power circulation device 300 to circulate the feed liquid through the double-sided conductive filter membrane 110. The power circulation means is not particularly limited and may include, for example, a peristaltic pump, a rubber hose, etc., so that the peristaltic pump and the feeding chamber 120 are connected by the rubber hose to form a circulation system.
In some embodiments, the DC power supply applies a constant voltage of 1-5V to the double-sided conductive filter 110 in step S22, considering that electrolytic water side reaction occurs at a higher voltage, which reduces Faraday efficiency. The water purifying effect and the use safety can be ensured by the low voltage electricity, and the energy consumption of the conductive film is reduced.
Step S23: the treated feed liquid is output from the osmosis chamber 130, and rapid water purification is realized based on the synergistic effect of electrochemical redox reaction and membrane osmosis.
Based on the technical scheme, the low-energy consumption rapid water purification is realized by adjusting the parameters of the film surface sputtering thickness, the applied voltage, the water inlet permeation rate and the like, and the film material is free from pollution and does not need back flushing.
The following detailed description of the present invention is given by way of example only, and not by way of limitation.
Example 1
The embodiment provides an electrofiltration water purification method based on a double-sided conductive filter membrane, which comprises the following steps:
1. preparation of sulfamethoxazole simulated wastewater:
the solvent acetonitrile was mixed with a 10. Mu.M concentration of sulfamethoxazole solution to prepare sulfamethoxazole simulated wastewater.
2. Pretreatment of ceramic membranes:
the side of the ceramic film which was washed with ultrapure water for 5 times and immersed for more than 24 hours was covered with a sealing film.
Referring to fig. 1, a sputtering target of a confocal magnetron co-sputtering device was placed opposite to a ceramic film, and the sputtering angle was modulated to 45 ° and the sputtering distance was 16cm.
3. Preparing Pd-Pt-CM conductive filter membrane:
one surface of the ceramic film faces the prepared nano Pd target material, and the bias voltage of 40W is applied for 3nm min -1 Magnetron sputtering is performed at the deposition rate of (a). Sputtering Pt on the other surface of the ceramic film by the same method, wherein the deposition rate is 2.3nm min -1 The sputtering thickness is controlled to be 30nm, and the Pd-Pt-CM conductive filter membrane is prepared. And placing the Pd-Pt-CM conductive filter membrane in a sputtering chamber of a confocal magnetron co-sputtering device for a period of time to enable the metal material to be completely loaded on the surface of the membrane.
4. Connecting the conductive filter membrane with the chamber to obtain a double-sided conductive membrane filter assembly 100:
referring to fig. 2A, 2B and 3, the double-sided conductive membrane filter assembly 100 comprises a 12ml feed chamber 120, a 12ml permeate chamber 130, and a Pd-Pt-CM conductive filter membrane between the feed chamber 120 and the permeate chamber 130; pd-CM faced the feed chamber 120 and Pt-CM faced the permeate chamber 130. The outer periphery of the Pd-Pt-CM conductive filter membrane is provided with a sealing rubber ring 160, the annular conductive gaskets 150 and 150 'and the annular conductive sheets 140 and 140' are used for respectively connecting the Pt-CM and the Pd-CM to the anode and the cathode of a power supply, a power switch is started, the control voltage is 1.6V, and a universal meter monitors the current and voltage change in real time.
5. Connecting a circulating device;
referring to fig. 3, peristaltic pumps are hose-connected to the feed chamber 120 to form a loop that simulates the flow of wastewater parallel to the membrane surface. And degrading 50ml of sulfamethoxazole simulated wastewater by using the assembled double-sided conductive film filter assembly, and measuring the removal rate of the conductive filter film to the sulfamethoxazole to be 90.3 percent after full reaction.
Comparative example 1: single-sided Pd-CM cathode film
An electrofiltration water purification method based on a single-sided conductive filter membrane comprises the following steps:
1. preparation of sulfamethoxazole simulated wastewater:
the solvent acetonitrile was mixed with a 10. Mu.M concentration of sulfamethoxazole solution to prepare sulfamethoxazole simulated wastewater.
2. Pretreatment of ceramic membranes:
the side of the ceramic film which was washed with ultrapure water for 5 times and immersed for more than 24 hours was covered with a sealing film.
The sputtering target of the confocal magnetron co-sputtering device and the ceramic film are placed oppositely, the sputtering included angle is modulated to be 45 degrees, and the sputtering distance is 16cm.
3. Preparation of Pd-CM cathode film:
one surface of the ceramic film faces the prepared nano Pd target material, and the bias voltage of 40W is applied for 3nm min -1 And (3) performing magnetron sputtering at a deposition rate of 30nm to prepare the Pd-CM cathode film. And placing the Pd-CM cathode film in a sputtering chamber of a confocal magnetron co-sputtering device for a period of time to enable the metal material to be fully loaded on the film surface.
4. Connecting the Pd-CM cathode membrane with the chamber to obtain a double-sided conductive membrane filter assembly 100:
referring to fig. 2A, 2B and 3, the double-sided conductive membrane filter assembly is assembled as in example 1 with the Pd-CM cathode membrane between the feed chamber 120 and the permeate chamber 130; pd-CM faced the feed chamber 120, and a porous titanium mesh was placed as a counter electrode on the other side of the ceramic membrane, facing the permeate chamber. The sealing rubber ring 160 is arranged on the outer periphery of the Pd-CM cathode film, the porous titanium mesh and the Pd-CM are connected to the anode and the cathode of a power supply by using the annular conductive gaskets 150 and 150 'and the annular conductive plates 140 and 140', a power switch is started, the control voltage is 1.6V, and the current and voltage change is monitored by a universal meter in real time.
5. Connecting a circulating device;
referring to fig. 3, peristaltic pumps are hose-connected to the feed chamber 120 to form a loop that simulates the flow of wastewater parallel to the membrane surface. And degrading 50ml of sulfamethoxazole simulated wastewater by using the assembled double-sided conductive film filter assembly, and determining that the removal rate of the conductive filter film to the sulfamethoxazole is 35.6 percent after the full reaction.
Comparative example 2: single-sided Pt-CM anode film
An electrofiltration water purification method based on a single-sided conductive filter membrane comprises the following steps:
1. preparation of sulfamethoxazole simulated wastewater:
the solvent acetonitrile was mixed with a 10. Mu.M concentration of sulfamethoxazole solution to prepare sulfamethoxazole simulated wastewater.
2. Pretreatment of ceramic membranes:
the side of the ceramic film which was washed with ultrapure water for 5 times and immersed for more than 24 hours was covered with a sealing film.
And (3) placing a sputtering target of the confocal magnetron co-sputtering device and the ceramic film opposite to each other, wherein the sputtering included angle is modulated to 45 degrees, and the sputtering distance is 16cm.
3. Preparation of Pt-CM anode film:
one surface of the ceramic film faces the prepared nano Pt target material, and the bias voltage is 40W, and the thickness is 2.3nm min -1 And (3) performing magnetron sputtering at a deposition rate of 30nm, and preparing the Pt-CM anode film. The Pt-CM anode film was placed in the sputtering chamber for a period of time to allow the metallic material to be fully supported on the film surface.
4. Connecting the Pt-CM anode membrane with the chamber to obtain a double-sided conductive membrane filter assembly 100:
referring to fig. 2A, 2B and 3, the assembly of the double-sided conductive film filter assembly is the same as that of embodiment 1; the Pt-CM faces the permeate chamber 130, and a porous titanium mesh is placed on the other side of the ceramic membrane as a counter electrode, facing the feed chamber 120. The outer periphery of the Pt-CM anode film is provided with a sealing rubber ring 160, the Pt-CM and the porous titanium net are connected to the positive electrode and the negative electrode of a power supply by using annular conductive gaskets 150 and 150 'and annular conductive plates 140 and 140', a power switch is started, the control voltage is 1.6V, and a universal meter monitors the current and voltage change in real time.
5. Connecting a circulating device;
referring to fig. 3, peristaltic pumps are hose-connected to the feed chamber 120 to form a loop that simulates the flow of wastewater parallel to the membrane surface. 50ml of sulfamethoxazole simulated wastewater is degraded by the assembled double-sided conductive film filter assembly, and after full reaction, the removal rate of the Pt-CM anode film to the sulfamethoxazole is determined to be 12.5 percent.
Comparative example 3: single-side flow catalytic mode of double-sided conductive filter membrane
An electrofiltration water purification method based on a double-sided conductive filter membrane comprises the following steps:
1. preparation of sulfamethoxazole simulated wastewater:
the solvent acetonitrile was mixed with a 10. Mu.M concentration of sulfamethoxazole solution to prepare sulfamethoxazole simulated wastewater.
2. Pretreatment of ceramic membranes:
the side of the ceramic film which was washed with ultrapure water for 5 times and immersed for more than 24 hours was covered with a sealing film.
The sputtering target of the confocal magnetron co-sputtering device is placed opposite to the ceramic film, the sputtering included angle is modulated to 45 degrees, and the sputtering distance is 16cm.
3. Preparing Pd-Pt-CM conductive filter membrane:
one surface of the ceramic film faces the prepared nano Pd target material, and the bias voltage of 40W is applied for 3nm min -1 Magnetron sputtering is performed at the deposition rate of (a). Sputtering Pt on the other surface of the ceramic film by the same method, wherein the deposition rate is 2.3nm min -1 The sputtering thickness is controlled to be 30nm, and the Pd-Pt-CM conductive filter membrane is prepared. And placing the Pd-Pt-CM conductive filter membrane in a sputtering chamber of a confocal magnetron co-sputtering device for a period of time to enable the metal material to be completely loaded on the surface of the membrane.
4. Connecting the conductive filter membrane with the chamber to obtain a double-sided conductive membrane filter assembly 100:
referring to fig. 2A, 2B and 3, the double-sided conductive film filter assembly 100 is assembled as in embodiment 1; pd-CM faced the feed chamber 120 and Pt-CM faced the permeate chamber 130. And a sealing rubber ring 160 is arranged on the outer periphery of the Pd-Pt-CM conductive filter membrane, the annular conductive gaskets 150 and 150 'and the annular conductive sheets 140 and 140' are used for connecting the Pt-CM and the Pd-CM to the anode and the cathode of a power supply, a power switch is started, the control voltage is 1.6V, and a universal meter monitors the current and voltage change in real time.
5. Connecting a circulating device;
referring to fig. 3, peristaltic pumps are hose-connected to the feed chamber 120 to form a loop that simulates the flow of wastewater parallel to the membrane surface. The assembled double-sided conductive film filter component is used for degrading 50ml of sulfamethoxazole simulated wastewater, the water outlet of the permeation chamber is sealed, the solution is ensured to circularly flow in the feeding chamber only, after the full reaction, a solution sample in the feeding chamber is taken for measurement, and the result shows that the removal rate of the conductive filter film to the sulfamethoxazole is 4.2 percent.
Comparative example 4: infiltration mode of double-sided supported metal material
An osmotic water purification method based on double-sided load metal materials comprises the following steps:
1. preparation of sulfamethoxazole simulated wastewater:
the solvent acetonitrile was mixed with a 10. Mu.M concentration of sulfamethoxazole solution to prepare sulfamethoxazole simulated wastewater.
2. Pretreatment of ceramic membranes:
the side of the ceramic film which was washed with ultrapure water for 5 times and immersed for more than 24 hours was covered with a sealing film.
Referring to fig. 1, a sputtering target of a confocal magnetron co-sputtering device was placed opposite to a ceramic film, and the sputtering angle was modulated to 45 ° and the sputtering distance was 16cm.
3. Preparation of Pd-Pt-CM functional film:
one surface of the ceramic film faces the prepared nano Pd target material, and the bias voltage of 40W is applied for 3nm min -1 Magnetron sputtering is performed at the deposition rate of (a). Sputtering Pt on the other surface of the ceramic film by the same method, wherein the deposition rate is 2.3nm min -1 The sputtering thickness was controlled to 30nm to prepare a Pd-Pt-CM functional film. And placing the Pd-Pt-CM functional film in a sputtering chamber of a confocal magnetron co-sputtering device for a period of time to enable the metal material to be completely loaded on the film surface.
4. Connecting the Pd-Pt-CM functional membrane with the chamber to obtain a permeable membrane module:
referring to fig. 2A, 2B and 3, the assembly of the osmotic membrane module is similar to that of example 1; sealing rubber rings 160 are arranged on the outer periphery of the Pd-Pt-CM functional film, the Pd-CM faces the feeding chamber 120, the Pt-CM faces the permeation chamber 130, and annular conductive gaskets 150 and 150 'and annular conductive plates 140 and 140' are respectively arranged on the Pd-CM face and the Pt-CM face. However, the permeable membrane module is not connected to the positive and negative electrodes of the power supply.
5. Connecting a circulating device;
referring to fig. 3, peristaltic pumps are hose-connected to the feed chamber 120 to form a loop that simulates the flow of wastewater parallel to the membrane surface. And (3) percolating and removing 50ml of sulfamethoxazole simulated wastewater by using the assembled permeable membrane assembly, and after full reaction, determining results show that the functional membrane has no removal effect on sulfamethoxazole.
As can be seen from the comparison of the above-described example 1 and comparative examples 1 to 4, when the double-sided conductive filter membrane of the present invention is used for treating hardly degradable wastewater based on electrochemical cross-flow filtration, compared with the single-sided conductive filter membrane, the single-sided flow catalytic mode or the non-conductive permeation mode,very remarkable pollutant removal effect is achieved. This is because, for example, dissolved oxygen in the wastewater can undergo a reduction reaction at the Pd cathode to produce H 2 O 2 Plays a key role in the subsequent reaction, and the anode Pt-CM area will be mostly H 2 O 2 Oxidizing to generate a strong oxidizing active oxygen substance. In addition, according to different pollutants and the attached metals, the cathode can also generate reducing hydrogen with strong reducibility, and the reducing hydrogen stably exists in a way of forming a bond with noble metals, so that the cathode can be used for reducing common methods of reducing pollutants which are difficult to degrade, such as nitrate in water, high-toxicity chloride and the like.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.

Claims (12)

1. A method of electrically filtering clean water using a double-sided conductive membrane filter assembly, wherein the double-sided conductive membrane filter assembly comprises:
a double-sided conductive filter membrane comprising:
porous film substrate
Two layers of metal conductive coatings respectively formed on two surfaces of the porous film substrate and used as a cathode and an anode connected to an external power supply, wherein the metal conductive coatings are independently selected from Cu, pd, pt or Au;
the feeding chamber and the infiltration chamber are respectively arranged at two sides of the double-sided conductive filter membrane; wherein the metallic conductive coating as a cathode faces the feed chamber and the metallic conductive coating as an anode faces the permeate chamber;
two sets of electrically conductive connecting pieces, press from both sides respectively locate between two-sided electrically conductive filter membrane and the feed chamber and between two-sided electrically conductive filter membrane and the infiltration room, be used for with two-sided electrically conductive filter membrane with the external power source carries out the electricity and is connected, electrically conductive connecting piece includes:
an annular conductive gasket with one surface attached to the metal conductive coating, an
An annular conductive sheet, one surface of which is attached to the other surface of the annular conductive gasket, and the other surface of which is attached to the feed chamber or the infiltration chamber; and
the sealing rubber ring is sleeved on the outer periphery of the double-sided conductive filter membrane and is used for preventing feed liquid in the feed chamber and the infiltration chamber from seeping out from the outer periphery of the double-sided conductive filter membrane;
the method comprises the following steps:
connecting the double-sided conductive filter membrane of the double-sided conductive membrane filter assembly to an external power supply through the two groups of conductive connecting pieces;
feeding a feed liquid into a feeding chamber, and carrying out electrofiltration treatment on the feed liquid by utilizing the double-sided conductive filter membrane under the electrifying condition, so that the double-sided conductive filter membrane generates active oxygen substances in situ to degrade organic pollutants in water based on the synergistic effect of electrochemical reduction and oxidation; and
and outputting the treated feed liquid from the infiltration chamber.
2. The method according to claim 1, characterized in that:
the side surface of the feeding chamber and the top surface opposite to the permeation chamber are respectively provided with a material hole;
the side surface of the infiltration chamber and the bottom surface opposite to the feeding chamber are respectively provided with a material hole.
3. The method of claim 1, wherein the annular conductive sheet has electrode posts extending therefrom for connection to the external power source.
4. The method of claim 1, wherein the porous membrane substrate is selected from one of a ceramic membrane, a polytetrafluoroethylene membrane, a polyamide membrane, and a polysulfone membrane.
5. The method of claim 1, wherein the thickness of the metal conductive coating is 10-60 nm.
6. The method of claim 1, wherein the two metal conductive coatings are sequentially formed on both surfaces of the porous membrane substrate using a physical vapor deposition method.
7. The method of claim 6, wherein the two metal conductive coatings are formed sequentially on both surfaces of the porous membrane substrate using confocal magnetron co-sputtering.
8. The method of claim 7, wherein the conditions of the confocal magnetron co-sputtering are: the base pressure in the sputtering chamber is 10 -7 Pa, argon gas provides an argon atmosphere at an operating pressure of 0.3 Pa; the sputtering angle between the metal sputtering target and the porous film substrate is controlled to be 20-40 DEG, and the distance is 15-20 cm; applying bias voltage of 20-60W and deposition rate of 1.0-5.0 nm min -1 。
9. The method according to claim 1, characterized in that:
the annular conductive gasket is conductive rubber, and the annular conductive sheet is stainless steel; and/or
The thickness of the annular conductive gasket is 0.2-2 mm; the thickness of the annular conducting strip is 0.5-2 mm.
10. The method of claim 1, wherein the feed solution flows through the double-sided conductive filter membrane in a cross-flow filtration or dead-end filtration mode.
11. The method of claim 10, wherein the filtration mode is switched by controlling the communication between the feed chamber and the permeate chamber feed orifice.
12. The method of claim 10, wherein the voltage applied to the double-sided conductive filter by the external power source is 1-5 v.
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